201040003 . 六、發明說明： 【發明所屬之技術領域】 本發明係一種注漿成型用之模具，尤其係—種用於成 型具有提高之緻密性的生胚，使其適用於製作大尺寸靶材 的模具。 【先前技術】 透明導電膜氧化銦錫（丨ndiUmTin〇xide)，簡稱為丨丁〇， 由於同時具有低導電度及高透光率的特性，目前已被廣泛 ©應用在顯示器的導電玻璃、太陽能電池以及電磁遮蔽玻璃 等方面。隨著顯示器畫面尺寸趨向大型化、高精密化，低 溫成膜、低f阻射生、高透光率及膜表面之平坦度均是|τ〇 技術發展的重點。 製備丨TO薄膜的主流技術是磁控濺射技術，其特點是 能使薄膜在低溫沉積下獲得優良的光學與電學性能，此外 還具有積速率尚、基片溫度低、成膜附著性好 '易控制、201040003 . VI. Description of the Invention: [Technical Field] The present invention relates to a mold for injection molding, in particular to a green mold for forming an improved compactness, which is suitable for producing a large-sized target Mold. [Prior Art] Transparent conductive film indium tin oxide (丨ndiUmTin〇xide), abbreviated as 丨丁〇, due to its low conductivity and high light transmittance, it has been widely used in conductive glass and solar energy of displays. Battery and electromagnetic shielding glass. As the screen size of the display tends to be large and high-precision, low-temperature film formation, low-resistance, high light transmittance, and flatness of the film surface are the focus of the development of |τ〇 technology. The main technology for preparing 丨TO film is magnetron sputtering technology, which is characterized by excellent optical and electrical properties of the film under low temperature deposition. In addition, it has a high rate of deposition, low substrate temperature and good film adhesion. Easy to control,
成本低、能大面積鍍臈等優點，目而成為應用最廣的 成臈技術。 ιτο 材的製作方法—般從原料粉末的選擇開始，接 著進行混粉、成型、燒結、加工以及接合。其中成型的方 去匕括塵模法或注聚成型法。壓模法的製程短、作業容易， 但不易製作大面積薄板，為了使生胚密度均句，通常粉末 必須經過造粒。而將 /製成型法的作業較複雜，所需的乾燥 時間長c 4合成型較複雜的形狀。通常以厘模法或是注 漿成型法成型後的生胚具有相對較低的密度，該生胚會先 以均壓設備提高生胚相對密度後再進行燒結、然而均壓設 3 201040003 .備昂貴且不易生產大型元件’因此應用層面無法擴大。 • 杈製過程中，通常需要添加加強粉末分散性之分散劑、 用以提高生胚強度之黏結劑、容易將生胚自模取出之脫模 劑、減少粉末相互摩擦之潤滑劑等。但是對高品質要求之丨丁〇 靶材來說，添加物的劑量越少越好，其原因除了可以減少 生產時的附加成本外，也可提高靶材的純度。 因此靶材成型技術開發的重點在於提高生胚密度、減 少添加物的劑量、尺寸大型化並且降低成本。尤其$降低 °成本的需求方面，注漿成型成為近年來技術開發的焦點。_ 以傳統的注漿成型法製作板狀生胚，通常係使用兩片以上 的石膏模具進行全面或是兩面的水份吸收，雖然可以加速 泥漿中的液體被吸收，縮短成型時間，但卻會造成產品甚 多的缺陷。不論泥漿從任何方向注入模具中皆會造成生胚 的流紋，進而影響燒結密度的均勻性，且泥聚中的液體被 多方向的吸力拉扯，容易使大型生胚中層粉末的黏結性較 差而產生分層剝離的現象；此外，石膏模具的吸水速度若 © 不一致，容易導致生胚内外層的乾燥程度不同，而在内部 形成空孔或凹陷，即使使用壓力注漿也無法完全解決。 相關文獻可參考JP2007-055055 ’其係有關於利用注 襞入口處的弧形設計改善脫模良率；jp1997_2721〇9，其 係有關於利用上蓋不吸水的設計解決成型體内部的缺陷， 以避免燒結時產生裂痕，但其側壁仍具吸水功能，故會造 成生胚的缺陷；TW548256，其係利用過濾式薄膜以減壓排 水的方式成型。 【發明内容】 4 201040003 本發明人為了改善全面或是兩面吸水模具所造成之產 品缺陷等問題，因此經過不斷的研究與努力後，終於發明 出此注漿成型用之模具。 本發明之目的係在於提供一種能用於製造出具有良好 生胚緻密度以用於製作大尺寸靶材之生胚的注漿成型用之 模具。 為達上述目的，本發明之一種注漿成型用之模具，其 係包括底部、側壁以及由該底部和側壁所圍成的一容納空 ©間，其中僅有該底部之材料為吸水性多孔質的材料，而該 側壁無法吸水。 +其中，該吸水性多孔質的材料係包括但不限制在石膏、 樹脂、高分子半透膜以及於所屬技術領域中具有通常知識 者所知悉的吸水性多孔質的材料。較佳的是，該吸水性多 孔質的材料為石膏。 其中，δ亥側壁係以非吸水性材質所組成，進一步而言 係以防水性材料所組成。 其中，該側壁係以與該底部相同材質所組成，且於該 側壁内侧設置有非吸水性材質所組成之隔板，進一步而言 該隔板係以防水性材料所組成。 該防水性材料係包括但不限制在塑膠片、金屬片、玻 璃片以及於所屬技術領域中具有通常知識者所知悉的防水 性材料。 本發月又關於-種生胚，其係使用上述注衆成型用之 模具所成型者，其中該生胚的相對密度大於5〇%。 本發明尚有關於一種製作|Τ〇把材的方法，其係包含 201040003 ί周漿、注漿成型、脫模乾燥和燒結之步驟，以獲得該丨丁 〇 乾材’其中注漿成型步驟係包括使用上述注漿成型用之模 具以成型生胚。 其中，該生胚的相對密度大於50%。 其中’該燒結步驟包括至少一次低溫預燒結以及至少 一次南溫燒結。 較佳的是，所述的高溫燒結係在氧濃度為95%以上的 氣氛中進行。 本發明還關於一種ΙΤΟ靶材，其係以上述方法所製得 者。 本發明係僅有底部係以吸水材質所組成，因此利用由 單一方向吸收水份的方式，一次完成注漿動作，不必陸續 添加衆料，如此可以提升粉末堆積的均勻性以及生胚的緻 密性，使燒結體不易碎裂變形，並更能應用於製作大尺寸 之板狀耙材。 【實施方式】 清參看第一圖所示’其係本發明注漿成型用之模具的 一實施例，其係由一底部（10)及側壁（20)構成，該底部（10) 之材料為吸水性多孔質的材料，用以吸收泥漿中的液體， 而a玄側壁（20)於一實施例中係以非吸水性材料所組成，其 僅用以形成生胚外型，非用以吸收泥漿中的液體。 明參看第二圖所示’其係本發明之另一實施例，其大 致與上述實施例相同，其不同之處在於側壁（2〇,)於此實施 例中係利用與底部。目同的材料所組成，並於該側壁(2〇。 内侧6又有非吸水性之隔板（21 )，以避免側壁（20，）方向之水 6 201040003 份吸收，此隔板（21)除了有隔絕水份吸收的功能之外，更 有輔助脫模的功能。 本發明又一實施例中，該側壁可由非吸水性材料所組 成，並於該側壁内側再設有非吸水性之隔板，以絕對避免 側壁吸收泥漿中的液體，又可幫助脫膜。The advantages of low cost and large-area enameling have become the most widely used technology. The method of making ιτο materials begins with the selection of raw material powders, followed by mixing, molding, sintering, processing, and joining. Among them, the molding method is a dust molding method or an injection molding method. The compression molding method has a short manufacturing process and is easy to handle, but it is not easy to produce a large-area thin plate. In order to make the density of the raw embryos uniform, the powder usually has to be granulated. The work of the /forming method is more complicated, and the required drying time is longer than that of the c 4 synthetic type. Usually, the green embryos formed by the stencil method or the grouting method have a relatively low density, and the raw embryos are first sintered by a pressure equalizing device to increase the relative density of the green embryos, and then the sintering is performed, but the pressure is set to 3 201040003. It is expensive and difficult to produce large components' so the application level cannot be expanded. • During the tanning process, it is usually necessary to add a dispersant that enhances the dispersibility of the powder, a binder that enhances the strength of the green coke, a release agent that easily removes the green embryo from the mold, and a lubricant that reduces the friction between the powders. However, for high-quality 丨丁〇 targets, the less the dose of the additive, the better, in addition to reducing the additional cost of production, but also improving the purity of the target. Therefore, the development of target molding technology focuses on increasing the density of green embryos, reducing the dosage of additives, increasing the size, and reducing costs. Especially in terms of the need to reduce the cost, grouting has become the focus of technology development in recent years. _ Producing plate-shaped embryos by traditional grouting method, usually using two or more gypsum molds for full or double-sided water absorption, although it can accelerate the absorption of liquid in the mud and shorten the molding time, but it will Causes a lot of defects in the product. No matter whether the mud is injected into the mold from any direction, the flow pattern of the raw embryo will be caused, which will affect the uniformity of the sintered density, and the liquid in the mud accumulation will be pulled by the multi-directional suction, which tends to make the adhesion of the large raw layer medium powder to be poor. In addition, if the water absorption speed of the plaster mold is inconsistent, the degree of drying of the inner and outer layers of the green embryo may be different, and voids or depressions may be formed inside, even if pressure grouting is not completely solved. For related literature, please refer to JP2007-055055 'which is about improving the demoulding yield by using the curved design at the entrance of the injection; jp1997_2721〇9, which is about solving the defects inside the molded body by using the design of the upper cover without water absorption to avoid Cracks occur during sintering, but the sidewalls still have a water absorbing function, which causes defects in the raw embryos; TW548256, which is formed by using a filter film to reduce water drainage. SUMMARY OF THE INVENTION 4 201040003 The present inventors have invented the mold for the injection molding after continuous research and efforts in order to improve the defects of the product caused by the full or double-sided water absorbing mold. SUMMARY OF THE INVENTION An object of the present invention is to provide a mold for injection molding which can be used for producing a green embryo having a good green density for producing a large-sized target. In order to achieve the above object, a mold for injection molding according to the present invention includes a bottom portion, a side wall, and a receiving space surrounded by the bottom portion and the side wall, wherein only the material of the bottom portion is water-absorbing porous material. The material does not absorb water. Here, the water-absorptive porous material includes, but is not limited to, a gypsum, a resin, a polymer semipermeable membrane, and a water-absorbent porous material known to those skilled in the art. Preferably, the water-absorbing porous material is gypsum. Among them, the δH side wall is composed of a non-absorbent material, and further composed of a water-repellent material. The side wall is made of the same material as the bottom portion, and a partition plate made of a non-absorbent material is disposed inside the side wall. Further, the partition plate is made of a water-repellent material. The water repellent material includes, but is not limited to, a plastic sheet, a metal sheet, a glass sheet, and a water repellent material known to those of ordinary skill in the art. This month's month is also related to the production of embryos which are formed by using the above-mentioned mold for molding, wherein the relative density of the green embryo is more than 5%. The invention further relates to a method for producing a enamel material, which comprises the steps of 201040003 ί weekly pulp, grouting, demoulding drying and sintering to obtain the 丨 〇 dry material 'where the grouting step is The use of the above-described mold for injection molding to form a green embryo is included. Wherein, the relative density of the green embryo is greater than 50%. Wherein the sintering step comprises at least one low temperature pre-sintering and at least one south temperature sintering. Preferably, the high-temperature sintering is carried out in an atmosphere having an oxygen concentration of 95% or more. The present invention also relates to a ruthenium target which is produced by the above method. In the present invention, only the bottom portion is composed of a water absorbing material, so that the pulverizing action is completed at one time by absorbing water in a single direction, and it is not necessary to continuously add a batch of materials, so that the uniformity of powder accumulation and the compactness of the green embryo can be improved. The sintered body is not easily broken and deformed, and is more suitable for producing a large-sized plate-shaped coffin. [Embodiment] Referring to the first embodiment, an embodiment of the mold for grouting of the present invention is composed of a bottom portion (10) and a side wall (20), and the material of the bottom portion (10) is a water-absorptive porous material for absorbing liquid in the mud, and the a-small side wall (20) is composed of a non-absorbent material in one embodiment, which is only used to form a green embryo, not for absorption. The liquid in the mud. Referring to the second embodiment, which is another embodiment of the present invention, it is substantially the same as the above embodiment, except that the side wall (2〇,) is utilized in the embodiment and the bottom. The same material is composed on the side wall (2〇. The inner side 6 has a non-absorbent partition (21) to avoid the absorption of water in the direction of the side wall (20,) 6 201040003, this partition (21) In addition to the function of isolating moisture absorption, it has the function of assisting demolding. In another embodiment of the invention, the side wall may be composed of a non-absorbent material, and a non-absorbent barrier is disposed on the inner side of the side wall. The plate, in order to absolutely avoid the side wall to absorb the liquid in the mud, can also help to remove the film.
藉由本發明係以單向吸水之模具進行靶材生胚的成 型’漿料中僅需添加微量的分散劑幫助粉末分散，並不需 要額外添加黏結劑或其他壓力注漿的設備，甚至不必經過 任何均壓製程，所得的生胚相對密度即可達到5〇%以上。 因此利用本發明除了能提升靶材純度外，更可大幅降低生 產成本。 成型後的生胚經過高溫燒結可以得到相對密度99%以 上之乾材。燒結過程中’當IT〇燒結體的溫度大於75代 時，例如常用的丨。2〇3會分解為丨…和〇2，在更高溫度下 1门2〇又會進一步再分解為丨 砰’這種分解行為會影響 乾材的緻密性以及導電性，為 ▼电1马了抑制分解的發生，本發明 將生胚在通氧的環境中進行階 一 Μ進仃階攸性的低溫預燒結，並在氧 浪度尚的氣氖中進行高溫燒結。 實施例： 製作注漿成型用之模具 膏模板係作為模具的底部，而外框:棋板及外框，該石 設於該石膏模板上以圍出—容納^為模具的側壁而立 尺寸需求製作，所圍出的容納’該外框係依據生胚 二間係用於盛裝泥漿，以在 7 201040003 石《模板上方框住泥漿以防止泥漿外洩；灌漿前以塑膠薄 .#置於外框之内侧，以阻絕外框吸收泥漿中的液體，並且 便於脫模。 調漿 使用氧化銦錫（ΙΤΟ)粉末調漿，粉末與水之混合比為 5.1，之後加入〇·3 wt%的分散劑，並無添加任何黏結劑， 進行球磨20小時’以調配出丨丁〇泥漿。 注漿成型 〇 將已調好的丨丁〇泥漿注入上述模具中，泥漿的重力產 生注漿成型的壓力，使泥漿内部的氣泡浮起，接觸空氣而 消失’因此可不需添加消泡劑。 脫模乾燥 將丨TO泥漿靜置，直到丨το泥漿中的液體被石膏模具 吸收後進行脫模及生胚乾燥’此時以阿幾米德法量測生胚 密度達4g/cm 3 ’換算其相對密度可達55%以上。 燒結 〇 將生胚在通氧的爐中進行9001預燒後，再於氧濃度 95%以上的氣氛中進行1 goo °c高温燒結，即可得到丨丁〇乾 材’其相對密度可達99.5%以上。其中，將ITO粒徑控制 在〇.5um以内，並控制漿料的黏度及流動性，於本實施例 中係使用常壓通氧燒結爐，以節省設備的投資費用。 比較例1: 製作注漿成型用之模具 如同實施例以石膏漿製作5公分（cm)厚的石膏模板及 8 201040003 外框，該石膏模板係作為模具的底部，而外框係作為模具 的側壁而立設於該石膏模板上以圍出-容納空間，該外框 係依據生胚尺寸需求製作，㈣出的容納空間係用於盛裝 泥漿，以在石膏模板上方框住泥漿以防止泥漿外洩。 調漿 使用與實施例相同的氧化銦錫（丨τ〇)泥漿。 注漿成型 丨丁〇泥漿注入上述模具中，泥漿的重力產 將已調好的By the invention, the forming of the target green body is carried out by using a one-way water absorbing mold. The slurry only needs to add a small amount of dispersing agent to help the powder to disperse, and does not need to add additional adhesive or other pressure grouting equipment, or even Any relative compression process, the relative density of the resulting raw embryos can reach more than 5%. Therefore, in addition to improving the purity of the target, the present invention can greatly reduce the production cost. The formed green body is sintered at a high temperature to obtain a dry material having a relative density of 99% or more. During the sintering process, when the temperature of the IT crucible is greater than 75 generations, for example, conventional crucibles. 2〇3 will be decomposed into 丨... and 〇2, and at a higher temperature, one door will be further decomposed into 丨砰'. This decomposition will affect the compactness and conductivity of dry materials. In order to suppress the occurrence of decomposition, the present invention performs the low-temperature pre-sintering of the raw embryo in the oxygen-passing environment, and performs high-temperature sintering in the gas enthalpy of the oxygen wave. Embodiment: A mold paste template for making a grouting mold is used as a bottom portion of a mold, and an outer frame is a chess board and an outer frame, and the stone is disposed on the plaster template to enclose a side wall of the mold and is required to be dimensioned. The enclosure contained in the enclosure is based on the raw embryonic two compartments used to hold the mud to block the mud on the template of the 2010 20103 stone to prevent the mud from leaking; before the grouting, the plastic is thin. # placed in the outer frame The inside is used to block the outer frame from absorbing the liquid in the mud and to facilitate demolding. The slurry was pulverized with indium tin oxide (yttrium) powder. The mixing ratio of powder to water was 5.1. Then, 〇·3 wt% of dispersant was added. No binder was added and ball milling was carried out for 20 hours. 〇 mud. Grouting 〇 Injecting the adjusted 丨丁〇 mud into the above mold, the gravity of the mud produces the pressure of the grouting, so that the bubbles inside the mud float and come into contact with the air and disappear. Therefore, no defoaming agent can be added. The mold release is dried, and the 丨TO slurry is allowed to stand until the liquid in the 丨το mud is absorbed by the plaster mold, and then demolded and dried by the embryo. At this time, the density of the raw embryo is measured by the azomid method to 4 g/cm 3 ' The relative density can reach more than 55%. Sintering sputum, the raw embryo is pre-fired in an oxygen-passing furnace, and then sintered at a high temperature of 95% or more in an atmosphere of 1 goo °c to obtain a dry material of 丨丁〇, whose relative density can reach 99.5. %the above. Among them, the ITO particle diameter is controlled to within 5 um, and the viscosity and fluidity of the slurry are controlled. In the present embodiment, a normal pressure oxygen sintering furnace is used to save equipment investment costs. Comparative Example 1: Making a mold for grouting molding As in the example, a gypsum slurry of 5 cm (cm) thick and a frame of 8 201040003 were produced in a gypsum slurry, the gypsum template was used as the bottom of the mold, and the outer frame was used as the side wall of the mold. And erected on the gypsum formwork to enclose the accommodating space, the outer frame is made according to the raw embryo size requirement, and (4) the accommodating space is used for holding the mud to block the mud on the plaster stencil to prevent the mud from leaking out. Pulping The same indium tin oxide (丨τ〇) slurry as in the examples was used. Grouting, the slurry of the mud is injected into the above mold, and the gravity of the mud will be adjusted.
❹ 生注漿成型的壓力’使泥漿内部的氣泡浮起，接觸空氣而 消失’因此可不需添加消泡劑。❻由於側壁與底部同時排 水’造錢液表面形成凹面，在排水過程中須再進行補浆。 脫模乾燥The pressure at which the slurry is formed is such that the bubbles inside the slurry float and come into contact with the air to disappear. Therefore, it is not necessary to add an antifoaming agent. ❻Because the side wall and the bottom are drained at the same time, the surface of the money-making liquid forms a concave surface, and the slurry must be replenished during the drainage process. Demoulding drying
將1丁0泥黎靜置，直到1丁0泥槳中的㈣心㈣I 吸收後進行脫模及生胚乾燥’此時以阿幾米德法量測生胚 密度達3.5g/cm3，換算其相對密度約49〇/^ 燒結 將生胚在與實施例相同的條件下進行燒結，得到叩 乾材之相對密度約94·5%’_面可觀察到明顯裂卜 且將把材破斷後可發現第-纽漿與㈣造成之不均^現 象。 比較例2: 製作注漿成型用之模具 9 201040003 . 的側壁而立設於該石膏模板上以圍出一容納空間，該外框 • 係依據生胚尺寸需求製作，所圍出的容納空間係用於盛裝 泥漿，以在石膏模板上方框住泥漿以防止泥漿外洩，另以 一片石膏板作為上蓋。 調漿 使用與實施例相同的氧化銦錫（丨丁0)泥漿。 注漿成型 將已調好的ΙΤΟ泥漿注入上述模具中，蓋上石膏上蓋。 Ο 此時侧壁、底部與上蓋同時排水。 脫模乾燥 將ΙΤΟ泥槳靜置，直到ιτ〇泥漿中的液體被石膏模具 吸收後進行脫模及生胚乾燥，此時可發現生胚結構鬆散， 以阿幾米德法量測生胚密度達3.3g/cin 3,換算其相對密度 約46%。 又 燒結 將生胚在與實施例相同的條件下進行燒結，得到丨IQ θ 靶材之相對密度約犯％，靶材表面可觀察到明顯裂痕及變 形，且將靶材破斷後可發現靶材内部有多處孔洞。 比較例中使用兩面以上可吸水的模具成型出相對密度 不到50%的生胚，使得利用該生胚所製成的|τ〇基板的相 對抢度不到95% ;而藉由本發明所提供之模具可以成型出 相=密度達55%的生胚，並且使得後續製程的成本降低， 月b讓所製成的丨丁〇乾材之相對密度高達99.以上，因 此解決既有存在已久的問題，而可供相關產業利用，以促 201040003 * 進產業發展。 - 【圖式簡單說明】 第一圖係本發明注漿成型用之模具一實施例的立體視 圖。 第二圖係本發明注漿成型用之模具另一實施例的側面 剖視圖。 【主要元件符號說明】 (10)底部 〇 (20)(201)側壁 (21)隔板 11Place 1 Ding 0 Mu Li to stand until the (four) heart (4) I in the 1 D 0 mud pad is released and release the embryo. 'At this time, the density of the raw embryo is 3.5 g/cm 3 by the albemide method. The relative density is about 49 〇 / ^ Sintering, the green embryo is sintered under the same conditions as the examples, and the relative density of the dry material is about 94.5%. The surface can be clearly cracked and the material can be broken. It was found that the first-new slurry and (four) caused the unevenness. Comparative Example 2: A side wall of a mold 9 for a grouting molding was formed on the gypsum formwork to surround a gypsum formwork, and the outer frame was made according to the size requirement of the raw embryo, and the enclosed space was used. In the mud, the mud is placed on the plaster template to prevent the mud from leaking out, and a piece of gypsum board is used as the upper cover. Pulping The same indium tin oxide (butadiene 0) slurry as in the examples was used. Grouting Molding The adjusted mud slurry is poured into the above mold and covered with a gypsum cover. Ο At this time, the side wall, bottom and upper cover are drained at the same time. The mold release is dried, and the mud slurry is allowed to stand until the liquid in the mud is absorbed by the plaster mold, and then the mold is released and the embryo is dried. At this time, the structure of the embryo is found to be loose, and the density of the embryo is measured by the adamide method. 3.3g/cin 3, converted to a relative density of about 46%. Further sintering, the green embryos were sintered under the same conditions as in the examples to obtain a relative density of about 丨IQ θ target, and significant cracks and deformation were observed on the surface of the target, and the target was found after breaking the target. There are many holes in the interior. In the comparative example, a mold having a relative density of less than 50% is formed using a mold having water absorption of more than two sides, so that the relative smash of the substrate made of the green sheet is less than 95%; and provided by the present invention The mold can form the raw body with the phase=density of 55%, and the cost of the subsequent process is reduced. The monthly density of the prepared dry material of the diced glutinous rice is as high as 99. Therefore, the solution has existed for a long time. The problem can be used by relevant industries to promote the development of 201040003 * into the industry. - BRIEF DESCRIPTION OF THE DRAWINGS The first drawing is a perspective view of an embodiment of a mold for injection molding of the present invention. The second drawing is a side cross-sectional view showing another embodiment of the mold for casting according to the present invention. [Main component symbol description] (10) Bottom 〇 (20) (201) Side wall (21) Partition 11